Process for producing telomer alcohols



iteei at 3,100,231 PRGCESS FOR PRODUCING TELOMER ALQQHOLS Max E. Roha and Warren L. Beears, Breclrsville, (lino, assignors to Goodrich-Gulf Qhernicals, line, Cleveland, (lhio, a corporation of Delaware No Drawing. Filed Mar. 30, 1959, Ser. No. 862 ,6493 11 Claims. (til. 260-532) This invention relates to telomer alcohols having from 8 to 30 carbon atoms in the hydrocarbon chains, and more especially to a novel process for producing at substantially atmospheric pressure such telomer alcohols, and comprises in substance starting with mixed alkyl aluminum chlorides, such as an alkyl aluminum sesquichloride, and by chain growth of ethylene units inserting hydrocarbon groups between the aluminum atom and a carbon atom of the original alkyl groups, which carbon atom is attached directly to the aluminum atom, and thus to build up organo-aiuminum telomers by lengthening the original alkyl chains of the starting mixed alkyl aluminum chlorides. The products resulting from the insertion of hydrocarbon groups from ethylene into mixed alkyl aluminum chlorides by chain growth, or telomerization, are herein referred to as organo-aluminum telomers, and the higher alcohols produced therefrom as telomer alcohols.

An object of this invention is to produce telomer alcohols of high quality in a unitary coordinated series of steps comprising the insertion at substantially atmospheric pressure by chain growth of ethylene units into mixed alkyl aluminum chlorides between a carbon atom of the hydrocarbon groups and the aluminum atom, thus producing organo-aluminum telomers having hydrocarbon chains containing from 8 to 30 carbon atoms, and then producing therefrom the telomer alcohols, all steps being 9 carried out at substantially atmospheric pressures and at room or moderate temperatures, in relatively short times, and in simple inexpensive non-pressure equipment that brings the cost of plant and equipment down to a point which makes the production of the telomer alcohols a practical commercial operation and that economically produces telomer alcohols having hydrocarbon chain lengths which can be controlled.

Heretofore, it has not been feasible to build hydrocarbon groups of the desired chain length into mixed alkyl aluminum chlorides by chain growth, or telomeriza tion, at substantially atmospheric pressure, in the manner hereinabove generally described, because, inter alia, of the following facts: first, the chain growth proceeds only to a slight extent, or not at all, when ethylene is brought into intimate contact with the mixed alkyl aluminum chlorides, and, second, the mixed alkyl aluminum chlorides exhibit a common property of organo-aluminum compounds of breaking down into free hydrocarbons, aluminum hydrides, and aluminum chlorides, which are unwanted by-products, facts which applicants have repeatedly demonstrated by test.

Applicants have discovered that, for commercial operations carried out at substantially atmospheric pressure, excellent results are obtained in the insertion of hydrocarbon groups in mixed alkyl aluminum chlorides by preliminarily activating the mixed alkyl aluminum chlorides in the following manner: first, thoroughly saturating the mixed alkyl aluminum chlorides with ethylene gas and, then admixing titanium tetrachloride into the ethylene saturated mixed alkyl aluminum chlorides to produce activated mixed alkyl aluminum chlorides.

Further, applicants have demonstrated by numerous tests that the order of the addition of the two activating agents, namely, ethylene and titanium tetrachloride, is material, and that the addition of the titanium tetrachloride to the mixed alkyl aluminum chlorides prior to the if? Qt saturating of the mixed alkyl aluminum chlorides with ethylene does not produce the effective activated alkyl aluminum chlorides of this invention, and that, to produce highly effective activated mixed alkyl aluminum chlorides, it is necessary first to saturate the mixed alkyl aluminum chlorides with ethylene and then to mix intimately therewith the titanium tetrachloride. In this way, the highly effective activated mixed alkyl aluminum chlorides of this application are produced.

In the invention of this application telomer alcohols are produced by a novel process that makes it possible to produce, from the activated mixed alkyl aluminum chlorides by gradual hydrocarbon chain growth, organoaluminum telomers having substantially any desired number of carbon atoms in the hydrocarbon chains, and to stop the chain growth at the point in the building up of the hydrocarbon chains which will provide organoaluminum telomers of the predetermined hydrocarbon chain length and to produce therefrom by novel catalyzed reactions telomer alcohols having the predetermined number of carbon atoms in the hydrocarbon chains.

In carrying out the process of this invention, there is first prepared the mixed alkyl aluminum chlorides, suitable for use in the present invention, which is an admixture of a dialkyl aluminum chloride, R A1Cl, and an alkyl aluminum dichloride, RAlCl in which R represents a hydrocarbon radical of short chain length, such as ethyl, propyl, butyl, hexyl, octyl, and the like. These mixed alkyl aluminum chlorides are commonly represented by the empirical formula in which R has the same significance as above indicated, and x and y are numbers whose sum totals 3. When x and y are equal, the empirical formula is written wherein R has the same significance as in Formula 1 above, X represents hydrogen or chlorine, and m and n are numbers whose sum totals 3 and of which it, but not in may be Zero, with a second difierent compound of the formula Y Al-Cl wherein Y is hydrogen or an alkyl radical of the scope of R above defined, h and k are numbers whose sum totals 3 and of which h, but not k, may be zero. Thus, an admixture of a compound of Formula 3 with a different compound of Formula 4 will produce the mixed alkyl aluminum chlorides of this invention.

Illustrative of the compounds within the Formula 3 above, where X is chlorine, are R -Al, -R Al--Cl, RAl--Cl and of the compounds of Formula 4 above are Al-C1 RAl-Cl and R AlC1.

It will be seen that certain combinations of a compound, of Formula 3, such as R AlCl, and a different compound of Formula 4, such as R-Al-Cl in equal molar proportions, form on admixture an alkyl aluminum sesquichloride of Formula 2, in which case the two compounds form the sesquichloride on admixture one with the other and without any needed interaction. On the other hand, the simplest compound of Formula 3, viz: R Al, and simplest compound of Formula 4, viz: Al-Cl when admixed in inert circurnambient fluid media, as in an inert hydrocarbon solvent under a blanket of nitrogen gas, readily react with the evolution of heat and gas, indicating an exothermic reaction between the alkyl aluminum and the aluminum trichloride, which is known to be or an alkyl aluminum sesquichloride of the Formula 2 above.

It will he understood that other methods of making the mixed alkyl aluminum chlorides may be employed, as by reacting an alkyl chloride with metallic aluminum, in the presence of an appropriate catalyst, thus:

The alkyl aluminum sesquichloride may also be prepared by the reaction of triethyl aluminum and anhydrous aluminum trichloride in inert circumambient fluid media, by a well known reaction:

Having produced the mixed alkyl aluminum chlorides, they are then activated so as to be eifective in the chain growth of ethylene molecules into the mixed alkyl aluminum chlorides between the aluminum atom and a carbon atom of the hydrocarbon radicals of the mixed alkyl aluminum chlorides.

This activation is accomplished by dispersing the mixed alkyl aluminum chlorides in an inert hydrocarbon solvent under a blanket of inert gas, and bubbling through the resulting liquid a stream of ethylene gas, the ethylene stream being continued until the mixed alkyl aluminum chlorides are thoroughly saturated with ethylene. During this period of saturating the mixed alkyl aluminum chlorides with ethylene, tests indicate that chain growth in the mixed alkyl aluminum chlorides does not take place. Then, titanium tetrachloride, which may be dissolved in an inert organic solvent, is added with stirring to the ethylone saturated mixed alkyl aluminum chlorides, resulting in the activated mixed alkyl aluminum chlorides of this invention.

The activated mixed alkyl aluminum chlorides, as has been above indicated, are capable of taking up ethylene to build into the activated mixed alkyl aluminum chlorides hydrocarbon chains of increased chain length, and thus to produce an activated organo-aluminum telomer. This is readily accomplished by bubbling a stream of ethylene through the activated mixed alkyl aluminum chlorides until the chain growth has increased the number of carbon atoms in the hydrocarbon chains to the desired chain length, thus:

wherein R, x and y have the same significance as above, N represents the number of ethylene molecules available for chain growth, and 2 represents the mean number of ethylene molecules built into each of the x hydrocarbon chains.

The activated organo-aluminum telomer, prepared as above described, is now ready for oxidation and hydrolysis to produce the telomer alcohol.

It is 'well known that normal organo-aluminum telomers, under the influence of the exothermically generated heat of oxidation, break down to a certain extent splitting off :free hydrocarbons, and that it is not practically feasible to separate out these free hydrocarbons from the telomer alcohols by fractional distillation because of closeness of the boiling points of the telomer alcohols and the free hydrocarbons.

With the activated organo-aluminum telomers of this invention, however, the splitting oil of the free hydrocarbons is inhibited to a degree and thus it is possible to produce telomer alcohols of higher quality, that is, with a lower proportion of free hydrocarbons.

"The oxidation of the activate-d organo-alurninum telomer is aifected by simply bubbling a stream of oxygen gas therethrough until no more oxygen is taken up, and then treating the oxidated activated organo-aluminum telomer with water, or a dilute inorganic acid, to produce commercial telomer alcohols of relatively high quality, which may 'be separated out by the usual means employed in such cases.

In brief, the invention of this application in its principal embodiment is directed to an economical unitary process :for producing telomer alcohols having from 8 to 30 carbon atoms directly from ethylene, in a unitary coordinated series of steps comprising producing an activated organo-aluminum telomer from activated mixed ethyl aluminum chlorides by building up therein by chain growth hydrocarbon chains of desired length to form an activated organo-aluminum telomer having hydrocarbon chains of the desired chain length, as from 8 to 30 carbon atoms in each hydrocarbon chain, oxidizing the organoaluminum telomer, and then hydrolyzing the oxidized organo-aluminum telomer to form the telomer alcohol having irorn 8 to 30 carbon atoms, or higher, as may be desired.

APPARATUS While the invention of this application is not limited to any specific apparatus for the carrying out of the process thereof, it may be advantageously carried out in a fluidtight reactor equipped with a reflux condenser, mechanical stirrer, thermometer, feed inlets for reactants, including an inlet to admit nitrogen to the reactor and a gas inlet to admit reactant gases to the bottom of the reactor, the gas inlet being equipped with a suitable gas meter to measure the quantity of gases admitted to the reactor, and a gas outlet from the condenser equipped with a suitable gas meter to measure the quantity of gases discharged from the reactor through the reflux condenser. The reactor is also provided with means for the temperature control of, both to heat and to cool, the reactor contents.

The apparatus should first be purged of all air and moisture. This may be done by heating the reactor and at the same time passing dry nitrogen gas therethrough to remove any absorbed moisture and discharging the gases and vapors. This may be done also by passing dry nitrogen through the reactor over a considerable period of time, as overnight, to assure complete displacement of air and moisture in the apparatus with dry nitrogen. The gas outlet from the condenser with the gas meter therein is at all times open to the atmosphere, so that a slight positive pressure of nitrogen gas keeps the apparatus filled with the dry nitrogen gas by a slow flow of the gas therethrough. When so purged of air and moisture and while filled with dry nitrogen gas, the apparatus is ready for carrying out the process of this application.

Example I Utilizing the apparatus above described, purged of air and moisture and while maintaining a positive nitrogen pressure in the reactor at room temperature, charge into the reactor 19.22 grams of mixed ethyl aluminum chlorides in milliliters of dry xylene, the mixed ethyl aluminum chlorides being such as are prepared by the reaction in xylene of 8185 grams (0.066 mole) of anhydrous aluminum trichloride with 10.37 grams (0.091 mole) of triethyl aluminum, and resulting in an ethyl aluminum sesquichl'oride of the general formula (C H AlCl in which x and y are numbers whose total is 3 and Whose values range from 1.2 to 1.8. Seal the reactor. Stir the reactor contents for several minutes and then bubble ethylene gas through the reactor contents with stirring to thoroughly satunate the reactor contents with ethylene, an operation that may take as long as an hour. Alternatively, bubble ethylene through the reactor contents for about minutes While heating to 120 C. and while cooling to room temperature, a procedure which shortens the time necessary to effect saturation with ethylene of the mixed ethyl aluminum chlorides, this pro-saturation with ethylene being absolutely essential to the production of high yields of telomer alcohols by the process of this invention. Next add to the reactor contents with stirring 8 milliliters of titanium tetrachloride solution containing 0.2 millimole of titanium tetrachloride per cc. of solution, or 0.0016 mole of titanium tetrachloride, which may also be added directly without being placed in solution. Let the reactor contents stand for several minutes and dilute to 300 milliliters volume with dry xylene, prefcr ably with stirring.

Now bubble ethylene gas in a stream through the reactor contents, recording at frequent intervals from the inlet gas meter the inlet volume of ethylene gas to the reactor and from the outlet gas meter the outlet volume of gas from the reactor, the difference in volumes measuring the amount of ethylene gas taken up in chain growth by the hydrocarbon chains of the ethyl aluminum sesquichloride. The reactor contents may be maintained at about room temperature as about 20 C. to C., but a somewhat faster take up occurs at moderately elevated temperatures, temperatures as high as from 100 C. to 125 C. having been found to be satisfactory. From the tabulated measurements of the volume of ethylene gas admitted and of volume of gas discharged can be calculated the mean length of the hydrocarbon chains in the resulting organo-aluminum telomer. The following table includes the recordings and calculations of the ethylene take-up.

It is to be noted from the above tabulations and oalculaticns made thereon that the mean number of carbon atoms can be determined at any stage and the flow of ethylene to the reactor cut at such stage as will yield the desired mean number of carbon atoms in the built-up hydrocarbon chains.

From the above Table I it will be noted that at the end of 128 minutes the mean length of the built-up hydrocarbon chains is C indicating that an organo-aluminum telomer which is an n-eicosanyl aluminum telome-r has been produced. It was at this point that the stream of ethylene gas was cut off.

Now while maintaining the reactor contents at about room temperature, as up to about 25 C., bubble oxygen in a continuous stream through the reactor contents, preferably with stirring, until the oxidation has gone as far as it will go, which is shown by a substantially equal flow of oxygen gas through the inlet and outlet gas meters, these values being obtained by recording at intervals the inlet volume of oxygen passing through the inlet gas meter and the outlet volume of gas passing through the outlet gas meter and computing the oxygen take-up, as indicated in the following table:

TABLE II Liters Liters Time in Min. Temp, 0 Liters O2 in Oz out oxygen taken up Experience has shown that oxidation of the organoaluminum telomer is never absolutely complete, no matter how much oxygen is bubbled through the reactor contents, and that the presence of the catalyst titanium tetrachloride in the reactor contents enables higher yields of the oxidized organo-aluminum telomer to be attained than is obtained without the presence of titanium tetrachlo-ride.

Now add to the reactor contents 15 milliliters of HCl (50% excess) in 75 grams of water, with stirring, to hydrolyze the oxidized organo-aluminum telomer. Then, place the reactor contents in a separation funnel and allow two layers to separate out, a lower water layer and an upper organic layer. The organic layer is isolated, washed twice with water and afterward with a saturated solution of NaHCO The washed organic layer is then fractionally distilled under vacuum and the cut containing the n-eicosanyl alcohol, or n-eicosanol, a telomer alcohol of the formula C H OH is collected. This is a white waxy solid having a melting point or about 71 C., a boiling point of about 220 C. at a pressure of 3 mm., and a molecular Weight of 298.

The molar ratios of the mixed alkyl aluminum ch1o rides to the titanium tetrachloride catalyst is not critical and may be varied widely, but preferably range from 50:1 to 400:1, although higher or lower ratios may be satisfactorily employed, the molar ratio in the above Example I being about :1.

The production of telomer alcohols in the process of this invention is preferably carried out in inert circumambient fluid media, both liquid and gaseous, that are practically non-reactive with the mixed alkyl aluminum chlorides, the organo-aluminum telomer and with oxygen. The inert or non-reactive liquid media acts as dispersant and diluent for the reactants and is an inert liquid hydrocarbon, such as a satuated alkalne, among which are butane, pentane, hexane, heptane, octane and the like, or mixtures of alkanes such as Deobase kerosene, or the mixture of alka-nes resulting from the Fischer-Tropsch process, or a cycloalkane, such as cyclopentane, cyclohexane, methvlcyclopentane, methylcyclohexane, and the like, or a benzene hydrocanbon, such as benzene, toluene, xylene and the like, or any mixtures of them. The inert gaseous media are nitrogen, helium, argon, and like inert gases.

The amount of the non-reactive liquid medium is not critical, since it may be omitted and the reaction carried out initially under a blanket of non-reactive gas, and since it acts primarily as a diluent and as a regulator of the reaction. A ratio of 2:1 of inert liquid hydrocarbon to the mixed alkyl aluminum chlorides has bene found to give satisfactory results. However, the ratio of 1:1 facilitates a more rapid reaction, while higher ratios of 3-511 occasion a somewhat slower reaction. The amount of the inert liquid hydrocarbon may be varied to yield optimum results in any specific case.

The temperature at which the several reactions of the process of this invention are carried out is also not critical. Where the reaction temperature is kept low, as 5 C., the reactions proceed at a somewhat slower rate,

while at a higher temperature, up to the boiling point of the nonreactive liquid medium, it is possible to remove the exothermically generated heat in such way as to maintain the temperature of the reactor contents within constant limits. Experience to date indicates that near room temperatures, say about C. to 30 C., are satisfactory, and that higher temperatures up to the boiling point of the liquid medium may be employed, when it is desired to shorten the time of any reaction.

Example II The procedure of Example I is vfollowed as described therein except that the chain growth is stopped at the end of 51 minutes (see Table I) so as to produce an organoaluminum telomer having hydrocarbon chains of C length. The process of Example I is then continued to produce a telomer alcohol having 12 carbon atoms. This alcohol is ndodecyl alcohol, or n-dodecanol, C H O'H, commonly known as laurel alcohol, and is a leaflike crystalline solid, when crystallized in dilute ethyl alcohol, having a boiling point of 255 C., and a molecular weight of 186.

Example III Carry out the procedure of Example I in the manner indicated in Example H, but stopping the chain growth at the end of 9 3 minutes (Table I) so as to produce an organo-aluminum telomer having hydrocarbon chains of C length, there is similarly produced an n-hexadecyl alcohol, or n-hexadecanol, C H OH. This alcohol, commonly known as cetyl alcohol, is a crystalline solid having a melting point of about 49 C. and a molecular Weight of about 242.

Example IV Proceeding as in Example 111, but stopping the chain growth at the end of 115 minutes (Table I) to produce an organo-aluminum telomer having hydrocarbon chains of C length, there is similarly produced n-octadecyl alcohol, or n-ioctadecanol, C H OH. This alcohol, commonly known as stearyl alcohol, is a crystalline solid having a melting point of around 59 C. and a molecular weight of about 270.

Example V Following the procedure of Example I, but continuing the chain growth of ethylene molecules into the hydrocarbon chains of the ethyl aluminum sesquichloride until vorgano-alurninum telomers having hydrocarbon chains of C length are produced, there is produced a telomer alcohol having 26 carbon atoms, namely, ln-hexacosanol, C H OH, known as ceryl alcohol, which has a melting point of about 79 C. and a molecular weight of about 382.

Example VI In a similar manner, proceeding as in Example I, and stopping the chain growth at the end of 20, 30, 74 minutes, n-hexanol, n-roctauol and n-tetradecanol have been produced. By carrying the chain growth to produce hydrocarbon chains of C length, there is produced the telomer alcohol, n-triacontanol, C H OH, having a melting point of about 865 C. and a molecular weight of about 439.

Example VII Utilizing the same purged apparatus and the same procedure as in Example I, place in the reactor, under a blanket of dry nitrogen and 'while maintaining a positive pressure of nitrogen in the reactor, 25.9 grams of triisobutyl aluminum sesquichloride, which is a clear colorless liquid, in about 200 milliliters of dry benzene, the triisobutyl aluminum sesquichloride being such as is prepared by the reaction of 8.1 grams (0.06 mole) of anhydrous aluminum trichloride and 17.8 grams (0.091 mole) of triisobutyl aluminum. Seal the reactor and stir the reactor contents for several minutes at room temperature. Bubble ethylene through the reactor contents. Then add to the reactor contents, preferably with stirring and heating the reactor contents, 3.6 milliliters of a benzene solution containing 0.25 millimole of titanium tetrachloride to 1 cc. of solution, in all 0.0009 mole of titanium tetrachloride. Now, bubble ethylene in a steady continuous stream slowly through the reactor contents, preferably while stirring, and record the volumes of gas at short intervals from the inlet gas meter and the outlet gas meter. As in Example I, from these recorded results and from computations made therefrom, the mean length of the hydrocarbon chains at any time may be substantially determined.

TABLE III Total ethylene Mean Time of reaction Inlet Out-let take-up length in min. meter meter of alkyl in liters in liters chains In liters In moles 0 0 0 0 C4 7. 3 2. 52- 4. 82 1. 96 Co 14. 2 4. 7 9. 5 3. 86 Ca 22. 8 7. 6 15. 2 6. 15 C10 31. 8 11. 8 20.0 8.1 C12 40. 5 15. 35 25.15 10. 06 C14 48. 2 18.0 30. 2 12. 4 Cm It is to be noted from the above tabulation and cal cul'ations made thereon that the mean number of carbon atoms in the grown hydrocarbon chains can be approximated at any stage of the chain growth, and the addition of ethylene stopped. In the above Example VII, it was the purpose to obtain an organo-aluminum telomer in which the mean length of the built-up hydrocarbon chain is C or an organo-aluminum telomer which is a hexadecyl aluminum telomer from which the telomer alcohol, hexadecyl alcohol, is produced.

Example VIII Telomer alcohols may be made by the procedure of Example I without the use of dry nitrogen gas and an inert liquid diluent, these circumambient media being employed largely to blanket the reactants from contact with air and moisture.

Utilizing the same apparatus as in Example 1, pass ethylene gas through the apparatus until all nitrogen, where used to purge, air and moisture have been removed from the apparatus, and while maintaining a positive pressure of ethylene in the reactor, charge the reactor with 137.8 grams of isobutyl aluminum sesquichloride, a clear mobile colorless liquid, and bubble ethylene gas through the isobutyl aluminum sesquichloride, preferably while stirring, to saturate the sesquichloride with ethylene and cut oil the flow of ethylene when the gas meters indicate saturation. Now add to the reactor 0.974 gram (0.0052 mole) of titanium tetrachloride, with the reactor contents preferably at about C., all with a positive pressure of ethylene in the reactor and preferably continuous stirring. Then again bubble ethylene gas in a steady stream slowly through the reactor contents and record at intervals from the inlet gas meter the volume of ethylene gas entering into the reactor and from the outlet gas meter the outlet gas volume. The recordings and computations of Table ill of the Example VII are applicable to the reaction of this Example VIII. However, in this Example VIII, the flow of ethylene gas was cut off at the end of 90 minutes, when the mean length of the built-up hydrocarbon chain was C and tetradecvl alcohol, C H OH, termed in the trade, myristyl alcohol, is produced therefrom.

Example IX In the above examples, the alkyl group of the mixed alkyl aluminum chlorides employed is either ethyl or butyl, the alpha-olefin is ethylene, and the telomer alcohols produced are those having an even number of carbon atoms. The process of this application is also operable to produce telomer alcohols having an odd number of carbon atoms by starting with the mixed propyl aluminum chlorides, or propyl aluminum sesquichloride, and building by chain growth ethylene units into the propyl radicals of the mixed propyl aluminum chlorides, thus producing telomer alcohols having an odd number of carbon atoms, as from 5 to 31, and more, carbon atoms.

Thus, following the procedure of Example 5!, 22.16 grams of propyl aluminum sesquichloride in 90 milliliters of dry xylene is charged into a purged reactor, and ethylene gas is bubbled through the reactor contents to saturate the propyl aluminum sesquichloride with ethylene, then 0.0016 mole of titanium tetrachloride in solution in an inert solvent are added to the reactor contents and dry xylene added to bring the volume of the reactor contents to 300 milliliters, all with stirring. Then bubble ethylene gas in a slow steady stream through reactor contents containing the activated propyl aluminum sesquichloride, measuring and recording both inlet volume of ethylene gas and volume of gas discharged from the reactor, calculating the number of ethylene units taken up in chain growth by the activated propyl aluminum sesquichloride and cutting of]? the stream of ethylene gas to the reactor when the desired number of carbon atoms have been built into the propyl aluminum sesquichloride. These may be tabulated as in Table I, right-hand column, and read 3 5 7, 9 11 13, 15 17, 19, 21 et seq. In the way fully described in connection with Example I, and in Examples H to VI, telomer alcohols ranging from n-pentanol, n-heptanol, n-nonanol, n-undecanol, n-tridecanol, n-pentadecanol, n-heptadecanol, n-nonadecan01, n-heneicosanol, n-tricosanol, etc., to n-hentriacontanol, and higher telomer alcohols, are produced by the process of the invention of this application as exemplified in the preceding examples.

It will be seen from the description above that by the procedures of Examples I and IX, any telomer alcohol from a C alcohol to a C alcohol, and higher telomer alcohols, may be produced in accord with the invention of this application.

Example X While for satisfactory commercial operations, the procedures of the above Examples I to IX are adequate, as has been hereinabove pointed out, other alkyl aluminum sesquichlorides, such as pentyl, hexyl, heptyl and octyl aluminum sesquichlorides, may be employed in the process of this invention, and other alpha-olefins, such as propylene, nbultene, iso-butene, n-pentene, n-hexene and the like can be employed in the process of this invention, fiacts which have been amply demonstrated by tests.

Thus, (a) where ethyl aluminum sesquichloride and propylene are employed in the procedure of Example I, it has been demonstrated by test that a series of telomer alcohols, dilfering one from the next in the series by 3 carbon atoms, are produced, as pentanol, octanol, unadecanol, tetradecanol, heptadecanol, etc.; (b) where the propyl aluminum sesquichloride and propylene are employed in the procedure of Example I, a series of telomer alcohols, also difiering one from the next in the series by 3 carbon atoms, is produced as hexanol, nonanol, dodecanol, etc; where butyl aluminum sesquichloride and propylene are employed in the procedure of Example I, a series of telomer alcohols, also differing one from the next in the series by 3 carbon atoms, may be produced, as heptanol, decanol, tridecanol, etc.

It will be seen that the above combinations of ethyl, propyl and butyl aluminum sesquichlorides, and propylene as the alpha-olefin, produce a complete series of telomer alcohols having from to 31, and higher, carbon atoms.

hexyl, heptyl, and octyl aluminum sesquichlorides may be employed as the mixed alkyl aluminum chlorides and 10 ethylene, propylene, n butene and isobuty-lene, as the alpha-olefin, to produce telomer alcohols in a complete series in the same Way as described in the preceding Example X.

Thus, starting with mixed pentyl aluminum chlorides (a) where the alpha-olefin built by chain growth into the pen-tyl radical is ethylene, a series of telomer alcohols, dilfering one from the next in the series by two carbon atoms, and having hydrocarbon radicals of C C C C chain length, are produced; (b) where the alphaolefin is propylene, a series of telomer alcohols, differing one from the next in the series by three carbon atoms and having hydrocarbon radicals of C C C C C chain length, are produced; and (c) where the alpha-olefin is n-butene, a series of telomer alcohols, differing one from the other by four carbon atoms and having hydrocarbon radicals of C C C C C chain length, are produced.

Similarly, starting with hexyl aluminum sesquicbloiide, heptyl aluminum sesquichloride and octyl aluminum sesquichloride as the sesquichloride, and ethylene, propyln-butene as the alpha-olefin, telomer alcohols, similar to those described in the preceding paragraphs are produced.

It is recognized that in the process of producing these telomer alcohols of the above examples, in which the organo-aluminum telomer is made by the chain growth method, as described in Example I, the number of carbon atoms in each of the built-up hydrocarbon chains of the organo aluminum telomers varies somewhat. Thus, where the mean length of the hydrocarbon chains is Can the hydrocarbon chains are largely of C length, with the remainder being for the most part of C and C length. Thus, the resulting telomer alcohols, as produced in accordance with the process of this invention, are first a mixture of alcohols, from which the principal alcohol may be isolated, where desirable. Commercially, it is generally not necessary to isolate any one particular telomer alcohol, since the mixed telomer alcohols resulting in the processes of this invention are satisfactory for most purposes :for which these telomer alcohols are employed, and there is some indication that these mixed telomer alcohols may be even superior for certain purposes, such as the manufacture of plasticizers for natural and synthetic plastics and resins, and of detergents.

It is to be understood that modifications and variations in the procedure described herein may be made without departing from the spirit and scope of this invention. Due to the large number of combinations and embodiments which fall within the spirit of this invention, as set forth in the foregoing specification, the specific language, chemical compounds and examples are not intended to be in limitation of the invention. All modifications and variations that will occur to men skilled in the art are to be included, unless otherwise indicated, within the scope of the invention as disclosed in the specification and defined in the appended claims or their equivalents.

This application is a continuation-in-part of applicants earlier copending applications Serial No. 555,273, tiled December 27, 1955, now abandoned, and Serial No. 559,- 505, filed January 16, 1956, now U.S. Patent No. 2,977,- 381.

What is claimed is:

1. In a method of manufacturing telomer alcohol-s directly from alpha-olefin by a series of coordinated steps, all of which steps are carried out at substantially atmospheric pressures, the method which comprises (1) bringing mixed alkyl aluminum chlorides of the formula R AlCl in which R represents an alkyl radical having from 2 to 8 carbon atoms and x and y are numerical values whose sum totals 3, in inert circumambient media, into intimate agitative contact with a gaseous alpha: olefin having from 2 to 4 carbon atoms, at least partly to presaturate the mixed alkyl aluminum chlorides with the alpha-olefin gas; (2) then adding thereto with agitation titanium tetrachloride to produce activated mixed alkyl aluminum chlorides; (3) introducing into reactive contact with said activated mixed alkyl aluminum chlorides a gaseous alpha-olefin having from 2 to 4 carbon atoms to increase by chain growth the number of carbon atoms in the alkyl radicals or the said activated mixed alkyl aluminum chlorides to produce mixed alkyl aluminum chloride :te'lomers; (4) thereafter passing oxygen into intimate contact with the said mixed alkyl aluminum chloride telcmers to produce oxidized mixed alkyl aluminum chloride tel omers; and (5) finally adding a hydrolyzer selected from the class consisting of water and a dilute inorganic acid to convert the oxidized mixed alkyl aluminum chloride telomers to telomer alcohols.

2. The method as defined in claim 1 in which the alphaolefi-n is ethylene.

3. The method as defined in claim 1 in which the mixed alkyl aluminum chlorides are ethyl aluminum chlorides.

4. The method as defined in claim 1 in which the alphaolefin is ethylene and the mixed alkyl aluminum chlorides are ethyl aluminum chlorides.

5. In a method of manufacturing directly from ethylene telomer alcohols by a series of coordinated steps, all of which steps are carried out at substantially atmospheric pressures, the method which comprises (1) bringing ethyl aluminum sesquichloride of the formula in which x and y are numerical values whose sum totals 3 and whose values range from 1.2 to 1.8, into intimate agitative contact with ethylene gas to practically saturate the said sesquichloride with ethylene; (2) adding thereto with stirring titanium tetrachloride to produce an activated ethyl aluminum sesquichloride; (3) then introducing ethylene gradually into reactive contact with said activated ethyl aluminum sequichloride to build in by chain growth C H groups between a carbon of the ethyl groups and an aluminum atom of the said ethyl aluminum sesquichloride; (4) thereafiter passing oxygen in intimate contact with the built-up ethyl aluminum sesquichloride; and (5) finally adding thereto water to produce telomer alcohols.

6. In a method of manufacturing telorner alcohols directly :firom alpha-olefin by a series of coordinated steps all of which steps are carried out at substantially atmospheric pressures, the method which comprises (1) bringing mixed alkyl aluminum chlorides of the formula R -AlCl in which R represents an alkyl radical having from 2 to 8 carbon atoms and x and y are numerical values whose sum totals 3, in inert circumambient media into intimate agitative contact with a gaseous alpha olefin having from 2 to 4 carbon atoms, at least partly to presaturate the mixed alkyl aluminum chlorides with the alpha-olefin gas; (2) then adding thereto with agitation titanium tetrachloride to produce activated mixed alkyl aluminum chlorides; (3) introducing into reactive con- [tact with said activated mixed alkyl aluminum chlorides a gaseou alphamlefin having from 2 to 4 carbon atoms to increase by chain growth the number of carbon atoms in the alkyl radicals of the said activated mixed alkyl aluminum chlorides to produce mixed alkyl aluminum chloride telomers; (4) measuring the amount of the alphaolefin taken up in chain growth by the said activated mixed alkyl aluminum chlorides as the introduction of gaseous alphaaolefin proceeds and cutting oil the intro duction of gaseous alpha-olefin when a predetermined amount of the gaseous alpha-olefin has been taken up in chain growth; (5) thereafter passing oxygen into intimate contact with the said mixed alkyl aluminum chloride telorners [to produce oxidized mixed alkyl aluminum chloride telomers; and ('6) finally adding a hydrolyzer selected from the class consisting of Water and a dilute inorganic acid to convert the oxidized mixed alkyl aluminum chloride telomers to itelomer alcohols.

7. The method as defined in claim 6 in which the gaseous alpha-olefin is ethylene.

8. The method as defined in claim 6 in which the mixed alkyl aluminum chlorides are mixed ethyl aluminum chlorides.

9. In the manufacture from an alpha-olefin having from 2 to 4 carbon atoms of telomer alcohols having from 6 to 31 carbon atom v by first producing intermediate alkyl aluminum sesquichloride telomers in 1a coordinated series of steps, all of which are carried out at subst-antially atmospheric pressures, the process which comprises (1) bringing ethylene gas into agitation contact with a liquid admixture of an inert hydrocarbon liquid and an alkyl aluminum sesquichloride of the formula R -AlCl in which R is :an alkyl radical having from 2 to 8 carbon atoms and x and y are numerical values whose sum is 3 and whose values range from 1.2 to 1.8, until substantially no more ethylene :gas is taken up by the liquid admixture; (2) then adding thereto with agitation titanium tetrachloride to produce activated alkyl aluminum sesquichloride; (3) next introducing into reactive contact with said activated alkyl aluminum sesquichloride a gaseous alpha-olefin having from 2 to 4 carbon atoms to increase by chain growth the number of carbons in the alkyl radicals of said activated alkyl aluminum sesquichloride to produce alkyl aluminum sesquichloride rtelomers; (4) thereafter passing oxygen into intimate reactive contact with said alkyl aluminum sesquichloride telomers; and (5) finally adding thereto a hydrolyzing agent selected from the class consisting of water and dilute inorganic acid to convert the oxidized sesquichloride telomers to itelcmer alcohols.

10. The method as defined in claim 9 in which the alkyl aluminum sesquichloride is ethyl aluminum sesquichloride.

11. The method as defined in claim 9 in which the alpha-olefin is ethylene and the alkyl aluminum sesquichloride is ethyl aluminum sesquichloride.

References Cited in the file of this patent UNITED STATES PATENTS 2,826,598 Ziegler et :al Mar. 11, 1958 2,892,858 Ziegler June 30, 1959 FOREIGN PATENTS 534,792 Belgium Ian. 31, 1955 

1. IN A METHOD OF MANUFACTURING TELOMER ALCOHOLS DIRECTLY FROM ALPHA-OLEFIN BY A SERIES OF COORDINATED STEPS, ALL OF WHICH STEPS ARE CARRIED OUT AT SUBSTANTIALLY ATMOSPHERIC PRESSURES, THE METHOD WHICH COMPRISES (1) BRINGING MIXED ALKYL ALUMINUM CHLORIDES OF THE FORMULA RX-AI-CLY, IN WHICH R REPRESENTS AN ALKYL RADICAL HAVING FROM 2 TO 8 CARBON ATOMS AND X AND Y ARE NUMERICAL VAULES WHOSE SUM TOTALS 3, IN INERT CIRCUMAMBIENT MEDIA, INTO INTIMATE AGITATIVE CONTACT WITH A GASEOUS ALPHAOLEFIN HAVING FROM 2 TO 4 CARBON ATOMS, AT LEAST PARTLY TO PRESATURATE THE MIXED ALKYL ALUMINUM CHLORIDES WITH THE ALPHA-OLEFIN GAS; (2) THEN ADDING THERETO WITH AGITATION TITANIUM TETACHLORIDE TO PRODUCE ACTIVATED MIXED ALKYL ALUMINUM CHLORIDES; (3) INTRODUCING INTO REACTIVE CONTACT WITH SAID ACTIVATED MIXED ALKYL ALUMINUM CHLORIES A GASEOUS ALPHA-OLEFIN HAVING FROM 2 O 4 CARBON ATOMS TO INCREASE BY CHAIN GROWTH THE NUMBER OF CARBON ATOMS IN THE ALKYL RADICALS OF THE SAID ACTIVATED MIXED ALKYL ALUMINUM CHLORIDES TO PRODUCE MIXED ALKYL ALUMINUM CHLORIDE TELOMERS; (4) THEREAFTER PASSING OXYGEN INTO INTIMATE CONTACT WITH THE SAID MIXED ALKYL ALUMINUM CHLORIDE TELOMERS TO PRODUCE OXIDIZED MIXED ALKYL ALUMINUM CHLORIDE TOLEMERS; AND (5) FINALLY ADDING A HYDROLYZER SELECTED FROM THE CLASS CONSISTING OF WATER AND A DILUTE INORGANIC ACID TO CONCERT THE OXIDIZED MIXED ALKYL ALUMINUM CHORIDE TELOMERS ALCOHOLS. 